Method of concurrently dyeing and
imparting durable bioactive proper-
ties to synthetic textiles

ABSTRACT

DURABLE BIOACTIVE PROPERTIES ARE OBTAINED ON SYNTHETIC TEXTILE FIBERS AND FABRICS BY APPLYING AN AQUEOUS SOLUTION OR DISPERSION OF A COMPOSITION CONTAINING A DYE, A BIOACTIVE MATERIAL AND A CARRIER TO THE TEXTILE BY AN EXHAUSTION TECHNIQUE.

, 3,788,803 METHOD OF CONCURRENTLY DYEING AND IMPARTING DURABLEBIOACTIVE PROPER- TIES TO SYNTHETIC TEXTILES Stewart E. Klein, Harrison,N.Y., and D. Donald Gagliardi, deceased, late of East Greenwich, RJL, byFrances Dodge Gagliardi, executrix, East Greenwich, RL, assignors tosanitized Incorporated, New York, N.Y. No Drawing. Filed Nov. 2, 1971,Ser. No. 195,035 Int. Cl. D06p /18 US. Cl. 8-17 7 Claims ABSTRACT OF THEDISCLOSURE Durable bioactive properties are obtained on synthetictextile fibers and fabrics by applying an aqueous solution or dispersionof a composition containing a dye, a bioactive material and a carrier tothe textile by an exhaustion technique.

BACKGROUND OF THE INVENTION Numerous techniques have been proposed forthe'treatment of synthetic textile fibers or fabrics with materialshaving the ability to de-activate or kill microorganisms with which theycome into contact. Fibers or fabrics so treated are used in themanufacture of garments in order to prevent odor formation therein, tominimize the risk of skin rashes by contact therewith, and to otherwiseinhibit the spread of toxic organisms by such garments. The treatedfabrics are particularly useful in hospitals. Such treatments are alsowidely used for rot-proofing to protect synthetic textiles from attackby fungus, mildew and the like.

In the usual procedure for manufacturing fabrics, the raw fabrics orgriege goods are prepared and are thereafter bleached, dyed, and finallyfinished with water repellants, softeners and/or various resin finishes.Historically, bioactive agents generally have been applied to textilefabrics in the finish bath, along with other specialty finishes (e.g.,antistatic agents, softeners, water or stain repellants, etc.). However,when so applied, the bioactive material may be merely superficiallydeposited on the fabric surface, and when the fabric is subjected to themechanical manipulation of laundering and the emulsifying action of soapor detergents the bioactive residue may be released, leaving the fabricunprotected. Some bioactive materials applied by such finishingoperations may even be leached out by cold water or removed by otherweathering factors.

Various attempts have been made to impart improved durability totextiles treated with bioactive materials; see, for example US. Pat. No.3,547,688. Nevertheless, there still exists a need for a technique forimparting durable, broad spectrum bioactivity to synthetic textiles,which will inhibit gram-positive and gram-negative bacteria, fungi andthe like and which will be maintained even after repeated hightemperature alkaline washes.

Accordingly, it is the primary object of this invention to provide aprocess for economically imparting bactericidal, bacteriostatic,fungicidal and/ or fungistatic protection to synthetic textile fibers orfabrics, which bioactive properties persist after the textile isrepeatedly exposed to water leaching and subjected to multiplelaunderings. These and other objects will become apparent to thoseskilled in the art from the following detailed description.

SUMMARY OF THE INVENTION This invention relates to a method of impartingdurable bioactive properties to a synthetic textile, and, moreparticularly, relates to an improved method of imparting durablebioactive properties to synthetic textile fibers or fabrics by treatingthe same prior to finishing with an aqueous solution or dispersion of acomposition contain- United States Patent O ice ing a bioactive materialand a carrier therefor by the exhaustion technique. As distinguishedfrom conventional padding operations, application of thebioactive-carrier composition to the textile by exhaustion involves theuse of a closed systemin which the synthetic fibers or fabrics areimmersed in the treating bath for an extended period of time and underconditions sufficient to absorb the bioactive material into the textilefibers, effect fixation of the material to the fibers and exhaust thesame from the treatment bath. It has been found that by thus treatingsynthetic textiles with bioactive materials, rather than by applyingsuch materials by conventional padding techniques during textilefinishing operations, it is possible to provide bioactive properties ofmarkedly enhanced durability.

PREFERRED EMBODIMENTS OF THE INVENTION In accordance with the presentinvention, synthetic textile fibers or fabrics are treated with aqueoustreating baths, in solution or dispersion form, containing at least onesuitable bioactive material and a carrier therefor. By synthetic fibersor fabrics is meant those synthetic fibers, yarns, skeins or fabricscomprised wholly of synthetic polymeric materials, e.g., viscose,cellulose acetate or triacetate; or the nylons, polyesters, or vinylpolymers including polyolefins, acrylics and modacrylics, or the like;or blends of such materials with natural fibers such as cotton or othercellulosics, or wool or other proteinaceous materials.

As used herein, the term bioactive material comprehends those knowncategories of compounds which exhibit bacteriostatic, bactericidal,fungistatic, and/or fungicidal properties. Bioactive materials so usefulfor the treatment of textile fabrics include tin salts such as tributyltin oxide, tributyl tin neodecanoate, tributyl tin acetate, tributyl tinbenzoate, or tributyl tin salicylate.

Also useful in the treatment hereof are halophenols, such aspara-chloro-meta-xylenol, pentachlorophenol, 2,2- methylenebis(4-chlorophenol), 2,2'-methy1enebis(3,4,6- trichlorophenol), 5 chloro2(2,4 dichlorophenoxy) phenol, or the alkali metal salts thereof; aminessuch as anilides, particularly salicylanilide, tribromosalicylanilide,3,5-dibromo 3 trifiuoromethylsalicylanilide, trichlorocarbanilide, andtrifluorochlorocarbanilide; quaternary ammonium compounds such asalkyldimethylbenzyl ammonium chloride and alkyldimethylammoniumcyclohexylsulfamate; or thio compounds such asN-trichloromethylthio-4-cyclohexene-1,2-dicarboximide,

bis(dimethylthiocarbamoyl)disulfide,

trans-1,2-bis (n-propylsulfonyl) ethene,

bis(n-propylsulfonyl) ethene,

1,6-bis-(4-ethylmercaptophenylbisguanido)hexane,

hydroxypyridine-Z-thione,

3,5-dimethyl-tetrahydro-1,3,5,ZH-thiadiazine-Z-thione,

and

2,3,5,6-tetrachloro-4-(methylsufonyl) pyridine.

Additional bioactive materials which may be used herein includediphenylstibene Z-ethyl hexoate.

Yet other bioactive materials elfective against bacteria and/or fungi(see, for example, Antiseptics and Disinfectants, Fungicides andSterilization, edited by C. F. Reddish, 2nd ed., May 1961, chapter 13,pp. 308-313) may comprise the bioactive materials useful in thesynthetic textile treatment of the present invention, provided that suchmaterials are compatible with and inert with respect to the syntheticfibers or fabrics and any other additives which may be utilized inconnection with the dyeing, finishing, or other treatment thereof.

The carriers whose use is comprehended herein comprises those well-knowntypes of carriers normally employed as adjuvants to dyes in coloring oftextile fibers or fabrics. See, e.g., Brown et al., Halogenated Benzenesas Carriers for Dyeing Polyester Fibers, American Dyestuff Reporter,Apr. 22, 1968, p. 49. Carriers useful in the bioactive treatment of thepresent invention include phenols such as o-phenylphenol,p-phenylphenol, octylphenol, octylcresol and the like; aliphatic oraromatic esters such as butyl benzoate, benzyl benzoate, dimethylterephthalate, dimethyl phthalate, methyl salicylate, or mixtures ofsuch materials with various additives, e.g., mixtures of butyl benzoateand tripropyl phosphate; dimethyl terephthalate with benzanilide; ormixtures of the benzoic esters of aromatic alcohols, phenols ornaphtholswith an ether containing at least one aromatic radical (such asthe mixtures of benzyl benzoate and dibenzyl ether). Further usefulcarriers include halogenated aromatics, particularly halobenzenes suchas mono-, di-, and tri-chlorobenzenes, oor p-chlorobromo benzenes, ordibromobenzenes; aryl esters of carbonic acid such as diphenylcarbonate; cyclohexylamides of benzene sulfonic acids; or compoundscontaining one lactone group and one aromatic nucleus such as thelactone of 2-hydroxynaphthalene-ls-propionic acid. Other carriers usefulwith bioactive materials suitable for the treatment of synthetic fibersor fabrics in accordance herewith include biphenyl,et-mcthyl-naphthalene or the like.

The bioactive material is admixed with the carrier in the proportion offrom about to 35%? bioactive to 65 to 90% carrier, preferably from about20 to 25% bioactive to 75 to 80% carrier. The combined materials arethen incorporated in the synthetic textile treating bath for applicationprior to finishing of the fabric by an exhaustion technique. Asindicated hereinafter, the treatment bath may contain conventionalproportions of surfactants, dyestuffs or other materials utilized forthe treatment of synthetic textiles.

In particular, the bioactive material-carrier formulation is appliedfrom an aqueous treatment bath, i.e., Water or a mixture of water and apolar solvent, e.g., a lower aliphatic alcohol such as isopropanol. Asmall amount, for example, up to about 5 weight percent, and preferablyfrom about 1 to 3 weight percent, of a dispersing agent may additionallybe incorporated in the bath. Dispersing agents so useful include anionicsurfactants such as the alkali metal alkylbenzene sulfonates or longchain (8-20 carbon atoms) alkyl sulfates, e.g., the alkali metal saltsof dodecylbenzene sulfonate, lauryl sulfate, heptadecyl sulfate,diethylhexyl sulfate, tetradecyl sulfate, or ethylhexyl sulfate; andnon-ionic surfactants such as the alkylanddialkyl-phenoxypoly(ethyleneoxy)ethanols, preferably those having alkylmoieties of from 5 to 12 carbon atoms and l to 20 ethyleneoxy groups,e.g., octyl-, nonyl-, or dodecyl-phenoxypoly(ethyleneoxy)ethanols, fattyacid esters of polyhydric alcohols, e.g., glyceryl monostearate, or thelike.

The bioactive material-carrier formulation may additionally incorporateone or more dyestuffs conventionally used for the dyeing of syntheticfibers. In this manner, dyeing and bioactive treatment of the synthetictextiles may be accomplished in a single step and from the sametreatment bath. Any dyes conventionally employed for the dyeing ofsyntheic fibers may be so employed providing, of course, that theparticular dyestuff chosen is inert with respect to the bioactivematerial as well as the other constituents of the treatment bath.Dyestuffs so useful include those disclosed, for example, in Dyeing:Theory and Practice, Dyestuffs, vol. 42, Nos. 5-8, and Dyeing SyntheticFibers and Blends, 6th ed., General Aniline and Film Corporation.

Textile dyes are defined both by chemical composition and by method ofapplication. Dyes useful in the practice of the present invention maybelong to any of the following chemical classes: nitroso, nitro,monoazo, disazo, trisazo, polyazo, azoic, stilbene, diphenylmethane,triphenylmethane, xanthene, acridine, quinoline, methine, thiazole,indamine, indophenol, azine, oxazine, thiazine, sulfur, lactone,aminoketone, hydroxyketone, anthraquinone, indigoid, phthalocyanine, andnatural dyes (i.e., obtained from animal or vegetable matter with littleor no chemical processing such as curcuma, carmine, litmus, indigo,chlorophyll and walnut oil). Alternatively, the following classes ofdyestuffs, defined by mode of application, may be incorporated with thebioactive-carrier materials in the practice of the present invention:vat, sulfur, acid, disperse, developed, basic and reactive dyes. Ingeneral, any dyestuffs which may be applied to synthetic textile fibersor fabrics by exhaustion techniques may be used in conjunction with thepresent treatment so long as they are inert with respect to the otherconstituents of the treatment bah.

In accordance with the exhaustion technique hereof, the synthetictextile fibers or fabrics are immersed, prior to finishing, in thebioactive-carrier containing treatment bath within a closed system,generally for an extended period of time and under elevated temperatureconditions, to eeifct absorption and fixation of the bioactive materialwithin the fibers and thus exhaust the same from the bath. Generally, ithas been found necessary for the purposes of this invention to immersethe synthetic textile fibers or fabric within the bioactivematerial-containing treating bath for periods of from about 20 minutesto 3 hours at elevated temperatures. For such purposes, the use oftemperatures of from about 65 to 100 C., and desirably from about to C.,is particularly preferred to effect swelling of the textile fibers tofacilitate absorption and pick-up of the bioactive material.

The amount of the bioactive materials thus deposited on the textilefibers will vary, depending upon the particular bioactive component, thecarrier chosen, and the textile treated. In general, it is preferred todeposit from about 0.5 to 1.5, and most desirably about 0.5, pounds ofthe bioactive material per square yards of the final fabric product. Thebioactive material is thus deposited in amounts of from about 0.1 to0.5% by weight of the textile substrate. While greater amounts may beemployed, such has been found unnecessary to produce the desiredbioactive properties and is, of course, economically disadvantageous.

Upon removal of the synthetic textile fibers or fabrics from theexhaustion bath, the treated material may be dried and scoured inaccordance with conventional practice, and thereafter further processedin the manner known in the art, i.e., woven, knitted, or otherwiseplaced into the final piece goods if treated in the fibrous form, andthereafter subjected to finishing operations as usual.

The following examples illustrate various preferred embodiments of thepresent bioactive-carrier containing treating baths and the method oftreating synthetic textile materials therewith. It will be understoodthat the examples are illustrative and not limiting of the method andcompositions of the present invention. All parts and percentages aregiven by weight and all temperatures are indicated in degrees centigradethroughout the following exampes, the preceding general description andthe ensuing claims, unless otherwise specified.

EXAMPLES 1-l9 A first bioactive treatment composition (formulation A)was applied to various fabrics by placing wet-out fabrics by placingwet-out fabric swatches in a bath containing water and, as the bioactivematerial, 5-chloro- 2-(2,4-dichlorophenoxy) phenol (Geigys Irgasan DP-300). The bath temperature was about 40-50 C., which was maintained,with agitation, for 5-10 minutes to insure complete dispersion.Thereafter, 3 parts of a mixture of dimethyl phthalate as a carrier,isopropyl alcohol, and a non-ionic surfactant (Triton X-100), per partof bioactive agent, were added and the agitation maintained for anadditional 5-10 minutes. The bath temperature was thereafter raised toabout 95 100' C. (boiling) and maintained thereat for 1-2 hours. Thetemperature and period of immersion was such as to provide a pick-up ofabout 0.5% bioactive material based on the weight of the dry fabric. Theresulting treated fabrics were rinsed and dried, and labeled as havingbeen treated with Formulation A.

The foregoing was repeated except that one-half of the5-chloro-2-(2,4-dichlorophenoxy)phenol was replaced with an additionalbioactive material hexachlorophene-[2,2-methylenebis(3,4,6-trichlorophenol)], and the treated fabricslabeled as having been treated with formulation B.

Control formulations corresponding to test formulations A and B butexcluding the carrier were prepared by the addition of water, propyleneglycol, and Emulphor ON- 870 (a nonionic surfactant comprising apolyoxyethylated fatty alcohol having a melting point of 43 C., aspecific gravity at 25 C. of 1.03-1.04, a flash point of 238 C., and afire point of 343 C.) to the respective bioactive materials. Theresulting control formulations had the following compositions.

The control formulations were applied to individual fabric samples,either by the exhaustion technique described hereinabove or by paddingwith a 2-dip, 2-nip padder. The padding rolls were adjusted so as toprovide a pick-up of about 0.5% bioactive material based on the weightsof the dry fabrics treated. The samples thus treated were thereafterrinsed and dried in the same manner as the fabric swatches treated asaforesaid by the exhaustion technique.

The resulting fabric samples, treated by exhaustion or padding withbioactive material-containing formulations either incorporating orexcluding carrier materials, were thereafter tested for bioactivity bythe seeded agar plate test method AATCC 90-1965T, as described in the1966 Technical Manual of the American Association of Textile Chemistsand Colorists, vol. 40, 1968. In accordance with such test method, thevarious fabric samples were sterilized and thereafter placed on AATCCagar which had previously been seeded with test bacteria. Afterincubation, the samples were examined for bacterial growth; theexamination was repeated after plural launderings to determine thedurability of the antibacterial properties imparted to the respectivetextile samples. The presence of azone or halo. of antibacterialactivity (the region in which no growth of the text organism wasexhibited) was also determined in each instance.

The antibacterial properties imparted to the various syn- ;thetictextile fabric samples are tabulated in the following Tables IXI. Thetest fabrics whose antibacterial proper- .materials with the samebioactive compounds in the absence of the carrier by applying theformulation by padding or during finishing of the textile fabrics.

COMPARATIVE ANTIBACTERIAL ACTIVITY Mode of Number of launderings 4treat- Example or control l ment I 0 5 10 15 TABLE I.RAYON Example I(A)Example 2(B) Control A(I) Control B(I). Control C(II) Control D I) TABLEII.65% POLYESTE R/35% COTTON Example 3(A) E Example 4(B) E Control E(I)E Control F(I) P Control G(II) E $1 Control H(II) E TABLE III.50%WOOL/30% ACRYLIC/20% NYLON Example 5 A) E Control I(I E 1: E

Example 6(A) E Example 7(B) E Control K(I)-. E Control L(I) E-F ControlM(II) E Control N(II) E-F TABLE V.--% ACRYLIC/15% NYLON Example 8(A) EControl 0(1) E TABLE VI.70% POLYESTER/30% ACRYLIC Example 9(A)- v o aControl P(I) E Control Q,(I) E-F 4- TABLE VIL-ACETATE Example 10(A) EExample 11 13)-. E e c Control R(I E Control 8(1)-.. P Control 'I(II)- EControl U(II) P TABLE VIII.NYLON Example 12(A) E Example 13(B) E 0 oControl V(I) E 51 P E r? TABLE IX-ACBYLIC Example 14(A) 0 o Example15(B) 0 a .o Control Z(I) Control AA(I) Control AB(II) Control AC(II) PTABLE X.POLYESTER Example 16(A) Example 17(B) o l The examples areserially numbered from 1 to 19 and the controls are serially letteredfrom A to Z and AA to AK. The formulations tested in the respectiveexamples and controls are parenthetically referenced after the exampleor control number as Formulations A and B or Control Formulations I andII as identified above.

I The mode of application of respective formulations is identified bythe letters E and P," the former designating treatment of the gtelgegoods by exhaustion and the latter designating treatment duringfinishing by padding. The term E-F in Tables III, IV and VI designatestreatment of the test samples in the indicated control experiments bythe exhaustion technique during finishing of the samples.

8 In this experiment the treatment composition was applied to the grelgegoods by padding.

4 The symbols used to designate the bacterial growth after repeatedlaunderings are as follows:

+= Growth of test organism;

-=N o grqwth of test organism;

#=Imt1al nh1b1tion of growth of test organism; growth after a singlelaundering of test swatch;

=Sample exhibited zone (halo) of inhibition.

7 EXAMPLES 20-25 Bioactive material-containing formulations are'preparedin the manner described hereinabove by the admixture of 3 parts of themixture of dimethyl phthalate carrier, isopropanol, and a non-ionicsurfactant (Triton X-100) to one part of each of the following bioactivematerials.

Example: Bioactive material 20 3',4',5'-tribomosalicylanilide.

21 ch1oro-2-(2,4dichlorophenoxy)phe- 1101 (.4 part).

3',4,5'-tribromosalicylani1ide (.6 part).

22 5 chloro-2-(2,4-dichlorophenoxy)phen01 (.4 part);

3,5 dibromo-3'-trifluoromethy1salicylanilide (.6 part).

23 3,5 dibromo-3'-trifluoromethylsalicylanilide.

24 Zinc pyridmethione-N-oxide (.4 part); 3,4',5' tribromosalicylam'lide(.6 part).

25 Zinc pyridmethione-N-oxide.

It will be understood that various changes and modifications may be madein the method and compositions utilized in accordance with the presentinvention without departing from the spirit and scope thereof.Accordingly, the preferred embodiments of the invention describedhereinabove are solely intended to illustrate the invention and are notlimiting thereof.

What is claimed is:

1. In a method of imparting durable bioactive properties to synthetictextile fibers or fabrics, which comprises dyeing the textile, finishingthe same, and treating the textile with a bioactive material, theimprovement comprising:

treating the textile, concurrently with the dyeing there of, with thebioactive material by immersing the textile in a dyeing bath containingthe bioactive material and a carrier therefor; and

maintaining the textile in the dyeing bath within a closed system for anextended period of time and under temperatures sufficient to absorbsubstantially all of the bioactive materialinto the textile fibers,

etfect fixation of said material to the fibers, and

exhaust the bioactive material from the dyeing bath;

( 1) the bioactive material being a halophenol or an alkali metal saltthereof; and

8 (2) the carrier being an ester of terephthalic or phthalic acid.

2. The method of claim 1, wherein the synthetic textile is maintained inthe dyeing bath for a period and at temperatures sufficient to depositthe bioactive material on the synthetic textile in an amount of from 0.1to 0.5% by weight of the textile.

3. The method of claim 1, wherein the synthetic textile is immersed inthe dyeing bath for a period of from 20 minutes to three hours, whilemaintaining the bath at elevated temperatures.

4. The method of claim 3, wherein the dyeing Bath is maintained duringimmersion of the synthetic textile therein at temperatures of from to C.

5. The method of claim 1, wherein the bioactive material isparachloro-meta-xylenol, pentachlorophenol, 2,2- methylenebis(4-chlorophenol), 2,2-methylenebis(3,4,6- trichlorophenol),5-chloro-2(2,4-dichlorophenoxy)phenol or an alkali metal salt thereof;and the carrier is dimethyl terephthalate or dimethyl phthalate.

6. The method of claim 1, wherein the dyeing bath contains5-chloro-2-(2,4-dichlorophenoxy)phenol as the bioactive materialconstituent thereof, and dimethyl phthalate as the carrier therefor.

7. The method of claim 1, wherein the dyeing bath contains a mixture of5-chloro-2-(2,4-dichlorophenoxy) phenol and2,2'-methylenebis(3,4,6-trichlorophenyl) as the bioactive materialconstituent thereof, and dimethyl phthalate as the carrier therefor.

References Cited UNITED STATES PATENTS 1,879,351 9/1932 Lehmann 424-3082,880,129 3/1959 Billings 117--138.5 X 2,957,785 10/1960 Leatherland117-138.5 2,880,050 3/1959 Fortess et al 8--173 X 2,926,987 3/1960Freyerrnuth et al. 8-173 X 2,982,597 5/1961 Salvin et al 8-173 X3,101,236 8/1963 Salvin et a1 8-473 X 3,501,341 3/1970 Spange et a1117138.5

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US.Cl. X.R.

1l7138,5, 138.8 E, 138.8 F, 138.8 N, 138.8 VA

